EP2771408B1 - Composite particles, method for production thereof, and use thereof - Google Patents

Description

The present invention relates to composite particles comprising a support material and at least one pearlescent pigment, a process for their preparation and their use.

Pearlescent pigments are extremely dusty in dry powdery form. In order to simplify the handling of pearlescent pigments, for example during dosing, pearlescent pigments are offered in a solvent-moistened or pasty form. The disadvantage is that in these dosage forms solvent in the respective application, for example in paints, coatings, cosmetics, etc., can be registered.

As an alternative, pearlescent pigment granules are also available in which the pearlescent pigments are present with resins, binders, etc. in bound, and thus non-dusting, form. A disadvantage of this variant is that partially form agglomerates of pearlescent pigment granules, which do not completely disintegrate in the application. Also, due to the resins, binders, etc. used, incompatibilities with the respective application medium may occur.

The DE 10 2008 064 201 A1 relates to non-dusting pigment granules which are based on a carrier and are coated with effect pigments by means of an adhesion promoter. Adhesion promoters are aqueous emulsions, emulsions and dispersions based on acrylated polypropylenes and low chlorinated ones Polypropylenes or wax emulsions are used. The carrier material is partially or completely coated or coated with the effect pigment by the emulsion. According to the teaching of DE 10 2008 064 201 A1 For example, the mechanical properties of plastic-based carriers coated with aqueous adhesion promoters with platelet-shaped effect pigments, without pretreatment, such as corona discharge or flame treatment, are often inadequate. This manifests itself in particular in the form of dusty abrasion and loss of adhesion of the coating from the carrier substrate in the form of a delamination. A disadvantage of this variant is also that the adhesion promoter used can lead to incompatibilities in the application.

EP 1 520 876 A1 relates to a pigment preparation for plastics. DE 199 41 607 A1 relates to a pigment mixture containing BiOCl pigments. DE 103 13 663 A1 relates to a binder-containing high-gloss, non-toxic perglaze pigment preparation. US 2011/0112234 A1 relates to a pigment mixture. DE 10 2008 064 201 A1 relates to pigment granules.

The object of the present invention is to provide pearlescent pigments in a slightly or non-dusting form. In particular, the pearlescent pigments should be compatible with a wide variety of application media. Furthermore, this dosage form of pearlescent pigments should be accessible in a simple manner.

The object underlying the present invention is achieved by providing composite particles which comprise a carrier material and at least one pearlescent pigment, the carrier material and the at least one pearlescent pigment being bonded to one another without adhesive, the pearlescent pigment being present on the surface of the carrier material and on the carrier material not wrapped or encapsulated.

For the purposes of the invention, the term "without adhesive" means that the pearlescent pigments are not bound to the carrier material via a separately applied or arranged adhesive or a separately applied or arranged adhesion promoter. The need for a primer is used, for example, in DE 10 2008 064 201 A1 described.

Preferred developments are specified in the dependent subclaims 2 to 10.

• Mischen von Trägermaterial und wenigstens einem Perlglanzpigment, wobei das Trägermaterial eine wenigstens teilweise erweichte Oberfläche aufweist.

Furthermore, the object on which the invention is based is achieved by providing a method for producing the composite particles according to the invention, the method comprising the following step:

• Mixing of carrier material and at least one pearlescent pigment, wherein the carrier material has an at least partially softened surface.

The invention furthermore relates to the use of the composite particles according to the invention for coating substrates, preferably wallpapers or printed products, as well as in a coating material or as a coating material. The coating material can be paints, printing inks, paints and cosmetics. The cosmetic can be nail varnishes, creams, lotions, powders, etc. Preferably, the cosmetic is a nail polish.

In particular, the composite particles according to the invention are suitable for the optical finishing of substrates, in particular wallpapers, printed products, etc. The substrates, in particular wallpapers, printed products, etc., may already be printed or provided with patterns.

The inventors have surprisingly found that pearlescent pigments can be provided in dry and at the same time little or no dusty form if the carrier material and the pearlescent pigments are bonded to one another without adhesive.

In this case, a single pearlescent pigment or several pearlescent pigments may be bound to a carrier material. The carrier material is preferably formed particulate. Preferably, a plurality of pearlescent pigments are bound to a carrier particle. Preferably, the at least one pearlescent pigment or the pearlescent pigments are connected in largely planar contact with the carrier material. Depending on the size of the carrier particle, a multiplicity of pearlescent pigment particles, for example up to 100, up to 250 or up to 500 pearlescent pigments, can be applied and bonded to the carrier material, preferably carrier particles.

The proportion of pearlescent pigment, based on the total weight of the composite particles, is preferably in a range from 0.1 to 20% by weight, more preferably in a range from 0.2 to 15% by weight, more preferably in a range of 0.3 to 12 wt .-% and most preferably in a range of 0.5 to 8 wt .-%, each based on the total weight of the composite particles.

According to the invention, the pearlescent pigment lies on the surface of the carrier material and is not enveloped by it or not encapsulated. In this respect, the composite particle according to the invention fundamentally differs from a pigment preparation for the preparation of masterbatches.

By bonding the pearlescent pigments to the carrier material, preferably carrier particles, the pearlescent pigments can be handled with little dust, preferably dust-free. As a result of the carrier particles, the composite particles have such a high weight that, during the customary handling of pearlescent pigments, for example during metering, no substantial, preferably no, dust development occurs. Furthermore, in the case of the composite particles according to the invention, preferably no agglomeration occurs. Consequently, the composite particles according to the invention are preferably agglomerate-free.

Extremely advantageous composite particles according to the invention are low in dust, preferably dust-free, free-flowing and / or streubar. Thus, the composite particles according to the invention can be extremely advantageous, for example, on a substrate provided with adhesive and / or binder, for example a wallpaper or a printed product, sprinkled or applied by trickling, without causing a burden on man and the environment by a significant dust. Thus, the composite particles according to the invention offer considerable performance advantages. Low-dust or dust-free, yet free-flowing composite particles are also advantageous when incorporated in a printing ink.

According to a preferred variant of the invention, the pearlescent pigments are on at least one surface of the carrier material, preferably the carrier particles, firmly bonded. The cohesive bonding is preferably effected by an at least partial softening of the surface of the carrier material, preferably the carrier particles, and subsequent adhesion of the pearlescent pigments to the softened surface region. In the case of preferably only partially superficial softening of the carrier material, the surface becomes tacky so that the pearlescent pigments adhere to it. After the pearlescent pigments have adhered, the resulting composite particles are cooled, so that the surface of the carrier material, preferably the carrier particles, solidifies and solidifies. Thus, the pearlescent pigments are bonded to the carrier material, preferably the carrier particles, without a separate adhesive. The binding of the pearlescent pigments is thus effected by the carrier material.

The softening of the surface of the carrier material, preferably the carrier particles, is preferably effected by heat application or temperature increase. The solidification and solidification of the softened surface of the carrier material, preferably the carrier particles, by cooling or lowering the temperature. Upon heating of the carrier material, preferably the carrier particles, depending on the selected temperature and the composition of the carrier material, not only the surface, but the complete carrier material can be softened. The same applies, of course, also for the subsequent cooling process.

Of course, the surface of the carrier material, preferably the carrier particles, can also be dissolved and / or softened by treatment with a solvent, after which binding of the pearlescent pigments, preferably with drying or volatilization of the solvent, is made possible.

According to the invention, it is preferred to soften the surface of the carrier material, preferably the carrier particles, by applying heat.

The pearlescent pigments are therefore preferably bound exclusively by the softened and subsequently solidified or solidified carrier material or the material of the carrier particles.

Of course, composite particles according to the present invention can also be classified composite particles which can be obtained, for example, by sieving or by means of cyclones.

According to a preferred variant of the invention, the carrier material, which is preferably in the form of carrier particles, is platelet-shaped. Platelet-shaped means that the carrier material, preferably the carrier particles, is flat and has a nearly uniform, preferably uniform, thickness.

According to a further variant of the invention, the carrier materials, preferably carrier particles, are lens-shaped, spherical or irregular.

In a preferred embodiment, the support materials are platelet-shaped and polygonal. More preferably, the support materials are tetragonal, pentagonal, hexagonal, heptagonal, octogonal, nonagonal and / or decagonal. Tetragones, hexagons and / or octogones have proven to be very suitable polygons.

According to a further preferred embodiment, the platelet-shaped carrier material, preferably the carrier particles, has a uniform shape, for example a tetragonal or hexagonal or octagonal shape.

Tetragonal platelet-shaped carrier materials, preferably carrier particles, are rectangles, for example squares, rhombuses, parallelograms or trapezoids.

According to a further preferred development of the invention, the platelet-shaped carrier material, preferably carrier particles, has a hexagonal shape.

According to a further preferred embodiment, the platelet-shaped carrier material, preferably carrier particles, is present as a circular disk or as a wafer with a circular circumference.

In a further embodiment, the carrier materials are present in approximately spherical or lenticular form.

In a further embodiment, the carrier materials are present in approximately spherical shape.

In a further embodiment, the carrier materials are approximately lens-shaped.

According to a further variant of the invention, the carrier material, preferably carrier particles, is a plastic. Furthermore, it is preferred that the plastic is a thermoplastic or a thermoplastic elastomer.

The plastic may be a single-grade plastic or a mixture of different plastics, for example different polymers.

Consequently, according to a further variant of the invention, the plastic from which the carrier material, preferably the carrier particles, are manufactured, contains only a proportion of thermoplastic or thermoplastic elastomer.

It is advantageous if the plastic used as a carrier material, preferably carrier particles, thermoplastic material or thermoplastic elastomer contains or preferably consists thereof, since the surface can be softened or fused by heat so that the pearlescent pigments to the softened or partially melted surface can bind.

Suitable plastics or polymers may be, for example, polyethylene (PE), polypropylene (PP), polybutylene (PB), polyisobutylene (PI), polystyrene (PS), poly (meth) acrylates, e.g. Polymethylmethacrylate (PMMA), polyesters, e.g. Polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polycarbonate (PC), polyvinyl acetate copolymer (PVAC), polyvinyl chloride (PVC), ethylene acrylic acid copolymer (EAA), polyvinyl acetals, e.g. Polyvinyl butyral, polyvinyl butyral (PVB), polyvinyl alcohol (PVAL), polyolefins (PO), polyamide (PA), cellulose acetate (CA), cellulose acetobutyrate (CAB), cellulose nitrate (CN), cellulose triacetate (CTA), ethylene vinyl acetate (EVA), ethylene vinyl acetate copolymer , biodegradable polyesters, such as. As polylactic acid (polylactitol, PLA), polyethers, such as. As polyethylene glycol, polyacrylonitrile or mixtures thereof are used.

Preferred carrier materials, preferably carrier particles, are polyesters, such as e.g. As polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) and polyvinyl acetals, such as. As polyvinyl butyrals, polyvinyl butyral (PVB) or mixtures thereof.

Particular preference is given to using as carrier materials, preferably carrier particles, polyvinyl butyral (PVB) and polyethylene terephthalate (PET). Very particular preference is given to using polyethylene terephthalate (PET) as carrier material, preferably carrier particles.

According to a preferred variant of the invention, the plastics soften in a temperature range from 40 to 230 ° C, more preferably from 45 ° C to 190 ° C, even more preferably from 50 to 170 ° C. The softening temperature can also be referred to as glass transition temperature Tg. The glass transition temperature is determined by differential scanning calorimetry (DSC).

Support materials in hexagonal form and consisting of polyethylene terephthalate (PET) are available, for example, from RJA Plastics GmbH, 07989 Teichwolframsdorf, Germany, under the trade names Crystal Clear 0.008 "45.008E, Crystal Clear 0.016" 45.016E, Crystal Clear 0.025 "45.025E. Spherical or lenticular plastic carrier particles can be prepared by first melting the polymer or polymers and pelletizing it by granulation, e.g. B. underwater granulation, are brought to the desired particle size and shape by means of a perforated disc.

In a further embodiment, the carrier materials, preferably carrier particles, may be present as unevenly shaped polymers. For this purpose, the polymers can be used as polymer granules first by grinding, z. B. in a pin mill, ball mill or stirred ball mill, are brought to the desired particle size.

The carrier materials, preferably the carrier particles, are preferably transparent and uninearged. The transmitted or transmitted by the carrier materials amount of light consists of a directed and a diffuse component. If the light is scattered evenly in all directions, this causes a reduction in contrast and a milky-cloudy appearance. The so-called haze is defined as the amount of light in percent, which deviates on average by more than 2.5 ° from the incident light beam ( Byk-Gardner, Quality Control for Paints and Plastics, 2011/2012, p. 61/62 ). Preferably, in the case of the support materials to be used according to the invention, less than 15%, more preferably less than 10%, even more preferably less than 5% of the incident light deviates more than 2.5 ° from the incident light beam.

To achieve special color effects, it is also possible to use colored, single-sided or single-coated carrier materials.

For the production of colored platelet-shaped carrier materials, preferably carrier particles, it is possible to print a film, preferably before cutting the corresponding film, with a colored commercial binder for solvent-based gravure and flexographic printing inks. As dyed binders, polyesters, polyamides, PVC copolymers, aliphatic and / or aromatic ketone resins, melamine-urea resins, melamine-formaldehyde resins, maleinates, rosin derivatives, polyvinyl butyrals, casein or casein derivatives, Ethyl cellulose, nitrocellulose and / or aromatic and / or aliphatic polyurethanes or mixtures thereof, which are mixed with a colorant can be used. Polyvinyl butyral or polyurethane, which are mixed with up to 20% by weight of colorant, based on the total weight of the binder, are preferably used as the colored binder.
In a preferred embodiment, colored platelet-shaped support materials, preferably platelet-shaped hexagonal support particles, are prepared by, for example, gravure printing on a polyethylene terephthalate film, preferably before cutting the polyethylene terephthalate film, with a colored 25% by weight polyvinyl butyral binder.

Of course, it is also possible, in the production of platelet-shaped carrier materials, preferably carrier particles, for example hexagonal carrier particles, to use an already colored or colored foil from a film.

In a preferred embodiment, the platelet-shaped carrier material, preferably carrier particles, only consists of a polymer layer, which may optionally be coated with a surface additive.

The two surfaces of the platelet-shaped carrier material, preferably carrier particle, may consist of different materials. The carrier material, preferably carrier particles, in this variant is preferably produced from composite films which can be produced in a conventional manner, for example by coextrusion, lamination or extrusion coating.

Alternatively, one side of the carrier material, preferably in the form of a film, may be provided with a coating agent or surface additive.

According to the invention can be effected by the pearlescent pigments bind only on one surface of the carrier material, preferably carrier particles. For example, the coating agent or surface additive may have adhesion prevent the pearlescent pigments to the coated surface. The coating agent or the surface additive may, for example, be applied to a film surface before the carrier particles are produced from the film, for example by cutting, stamping, pressing, etc.

Likewise, composite films which are used to produce the carrier material, preferably in the form of carrier particles, may have a film surface to which pearlescent pigments can not be bound.

The selective bonding of the pearlescent pigments can be effected by virtue of the fact that the softening temperature of one surface of the carrier material, preferably of the carrier particles, differs from the softening temperature of the other surface, ie if only one surface is softened superficially at an applied temperature, and consequently only the softened surface bonds allowed by pearlescent pigments. If the binding takes place by dissolving the plastic using solvent, a selective bond to a plastic surface can be set via the different dissolving behavior of the plastic used in the respective layer.

A major advantage in the selective bonding of pearlescent pigments to only one surface of the carrier material, preferably carrier particles, is that the consumption of pearlescent pigments is halved.

Of course, according to a further embodiment of the invention, a two-sided occupancy of the carrier material with pearlescent pigment is possible. A two-sided occupancy may be desirable if a very intense pearlescent effect is desired.

Preferably, the carrier material or the carrier particles are substantially transparent, preferably transparent.

When applying the composite particles according to the invention to a substrate, for example wallpaper, printed product or fingernail, is transparent Support material, the orientation of the composite particles almost without significance. The optical effect of the pearlescent pigments is only slightly influenced by the carrier material.

Platelet-shaped support materials in polygonal or circular form, preferably hexagonal or rectangular in shape, can be made by cutting, stamping, pressing, etc. of plastic films or films. As a result, a uniform particle size can be ensured. Due to the manufacturing process, a small proportion of differently shaped or multiply cut particles can also be contained in the carrier material. However, this proportion is preferably not more than 15% by weight, more preferably not more than 10% by weight, more preferably not more than 8% by weight, still more preferably not more than 5% by weight, even more preferably not more than 3 wt .-%, each based on the total weight of the carrier material, so as not to affect the visual appearance of the composite particles in an application.

According to a preferred embodiment of the invention, platelet-shaped transparent support materials are used which have a polygonal shape, for example hexagonal or rectangular shape, or a circular shape, wherein the support materials can be provided on one side with a coating agent or a surface additive so that the pearlescent pigments do not adhere to the tie coated surface.

In another embodiment, differently shaped carrier materials, preferably carrier particles, the same or similar softening temperature can be used. The pearlescent pigments can thus be applied at the same time, for example, to support materials in platelet-shaped hexagonal form and support materials in approximately spherical form. The optical effects associated with composite particles based on a platelet-shaped hexagonal support material typically differ from the optical effects that can be achieved with composite particles based on an approximately spherical support material. In the case of composite particles based on an approximately spherical carrier material, the viewer is also outside the direct plan view, more pearlescent pigments facing than would be the case with composite particles based on a platelet-shaped hexagonal support material. For this, composite particles based on an approximately spherical support material appear in the plan view less highly lustrous than composite particles which have a platelet-shaped hexagonal support material. However, the gloss of composite particles based on an approximately spherical support material is significantly less dependent on the viewing angle than the gloss of composite particles based on a platelet-shaped hexagonal support material. Of course, in such a comparison, the particle sizes of the pearlescent pigments and the carrier material must be identical or at least comparable.

The particle size of the carrier materials, preferably platelet-shaped carrier particles, is preferably in a range of 50 to 2500 μm, more preferably in a range of 70 to 1600 μm, even more preferably in a range of 80 to 1000 μm, particularly preferably in a range of 100 to 800 microns and most preferably in a range of 180 to 450 microns.

Approximately spherical, lenticular or non-uniformly shaped carrier materials preferably have a particle size distribution. The D ₅₀ values of these support materials are preferably in a range of up to 100 to 3000 μm, more preferably in a range of 120 to 2500 μm, particularly preferably in a range of 150 to 2000 μm and most preferably in a range of 200 to 1300 μm.

If platelet-shaped carrier materials in polygonal form, preferably tetragonal or hexagonal, are used, their average thickness is preferably in a range of 5 to 150 μm, more preferably in a range of 6 to 140 μm, particularly preferably in a range of 7 to 130 microns and most preferably in a range of 11 to 120 microns.

If the platelet-shaped carrier material in polygonal form has an average thickness of at least 20 μm, not only the surface but also the cut edges of the carrier material can be coated with pearlescent pigments.

If lenticular support materials are used, their average thickness is preferably in a range of 5 to 500 μm, more preferably in a range of 6 to 450 μm, particularly preferably in a range of 7 to 370 μm, and most preferably in a range of 11 up to 350 μm. To determine the average thickness of the lenticular support materials, the largest value for the thickness of each individual particle is determined and averaged over at least 100 particles, as explained below.

The average thickness of the support materials can be determined by scanning electron micrographs of cross sections. In this case, preferably at least 100 individual particles are measured in order to obtain meaningful statistics.

To produce the composite particles according to the invention, pearlescent pigments based on non-metallic platelet-shaped substrates are used.

The non-metallic platelet-shaped substrates are preferably substantially transparent, preferably transparent, i. for visible light, they are at least partially, preferably substantially completely, permeable.

The non-metallic platelet-shaped substrates may be selected from the group consisting of natural mica flakes, synthetic mica flakes, glass flakes, SiO ₂ flakes, Al ₂ O ₃ flakes, BiOCl flakes, TiO ₂ flakes, Fe ₂ O ₃ flakes, sericite flakes, kaolin flakes , Graphite flakes, talc flakes, polymer flakes, platelet-shaped substrates comprising an inorganic-organic mixed layer are selected. Pearlescent pigments which can also be used according to the invention are those whose substrates are mixtures of the platelet-shaped substrates indicated above.

Preferably, the non-metallic platelet-shaped substrates are selected from the group consisting of natural mica flakes, synthetic mica flakes, glass flakes, SiO ₂ flakes, Al ₂ O ₃ flakes and mixtures thereof. More preferably, the non-metallic platelet-shaped substrates are selected from the group consisting of natural mica platelets, synthetic mica platelets, glass platelets, and mixtures thereof. Very particular preference is given to glass platelets and synthetic mica platelets and mixtures thereof as substrates. In particular, glass platelets are preferred as the substrate.

Natural mica flakes, in contrast to synthetic platelet-shaped transparent substrates, have the disadvantage that impurities due to intercalated foreign ions can change the hue, and that the surface is not ideally smooth due to the production, but irregularities, such as e.g. May have stages.

On the other hand, synthetic substrates such as glass flakes or synthetic mica platelets may have smooth surfaces and a uniform thickness within a single substrate particle, and preferably over the entirety of all substrate particles. Thus, the surface provides only little scattering centers for incident or reflected light and thus allows after coating these platelet-shaped substrates higher glossy and stronger color pearlescent than with platelet-shaped natural mica as a substrate. As glass slides, those are preferably used, which after the in EP 0 289 240 A1 . WO 2004/056716 A1 and the WO 2005/063637 A1 be prepared described methods. The glass plates which can be used as a substrate may, for example, have a composition according to the teaching of US Pat EP 1 980 594 B1 exhibit.

The non-metallic platelet-shaped substrate as described above may be provided with at least one layer or coating, the at least one layer preferably comprising metal oxides, metal oxide hydrates, metal hydroxides, metal suboxides, metals, metal fluorides, metal oxyhalides, Metal chalcogenides, metal nitrides, metal oxynitrides, metal sulfides, metal carbides or mixtures thereof. According to a preferred variant, the at least one layer or coating consists of the abovementioned materials.

Preference is given to using metal oxides, metal oxide hydrates, metal hydroxides and / or mixtures thereof as the layer or coating. Particular preference is given to using metal oxides and metal oxide hydrates and / or mixtures thereof. The aforementioned materials can be present either as separately separate layers or also side by side in the same layer.

The terms coating or coating are used interchangeably unless otherwise stated.

The coating can either completely encase the substrate, be present only partially on the substrate or cover only its upper and / or lower surface.

The at least one layer may be an optically active layer and / or serve as a protective layer.

If a high-index layer is applied to a non-metallic platelet-shaped substrate, then the refractive index is n ≥ 1.8, preferably n ≥ 1.9, and particularly preferably n ≥ 2.0. In the case of a low-refractive index layer or coating, the refractive index is n <1.8, preferably n <1.7 and particularly preferably n <1.6.

Suitable high-index layers are, for example, metal oxides such as titanium oxide, preferably titanium dioxide (TiO ₂ ), iron oxide, preferably iron (III) oxide (Fe ₂ O ₃ ) and / or iron (II / III) oxide (Fe ₃ O ₄ ), zinc oxide, preferably ZnO, tin oxide, preferably tin dioxide (SnO ₂ ), zirconium oxide, preferably zirconium dioxide (ZrO ₂ ), antimony oxide, preferably antimony (III) oxide (Sb ₂ O ₃ ), magnesium oxide, preferably MgO, cerium oxide, preferably cerium (IV) oxide (CeO ₂ ), cobalt oxide, preferably cobalt (II) oxide (CoO) and / or cobalt (II / III) oxide (Co ₃ O ₄ ), chromium oxide, preferably chromium (III) oxide (Cr ₂ O ₃ ), copper oxide, preferably copper (I) oxide (Cu ₂ O) and / or copper (II) oxide (CuO), vanadium oxide, preferably vanadium (IV) oxide (VO ₂ ) and / or vanadium (III ) oxide (V ₂ O ₃ ), metal sulfides such as zinc sulfide, preferably zinc (II) sulfide (ZnS), metal oxide hydrates such as goethite (FeOOH), titanates such as calcium titanate (CaTiO ₃ ) or iron titanates such. Ilmenite (FeTiO ₃ ), pseudobrookite (Fe ₂ TiO ₅ ) and / or pseudorutile (Fe ₂ Ti ₃ O ₉ ), doped metal oxides such as titanium dioxide and zirconia colored with selectively absorbing colorants, and / or mixtures thereof , The latter coloring of non-absorbing high-index metal oxides can, for. Example, by incorporation of colorants in the metal oxide layer, by doping with selectively absorbing metal cations or colored metal oxides such as ferric oxide or by coating the metal oxide layer with a colorant-containing film.

The high-index layer preferably comprises metal oxides, metal hydroxides and / or metal oxide hydrates. Particular preference is given to using metal oxides. Very particular preference is given to using titanium dioxide and / or iron oxide and mixtures thereof.

When coated with titanium dioxide, the titanium dioxide may be in the rutile or anatase crystal modification. The rutile form can be obtained, for example, by applying a layer of tin dioxide to the platelet-shaped substrate to be coated, for example, before application of the titanium dioxide layer. On this layer of tin dioxide, titanium dioxide crystallizes in the rutile modification. The tin dioxide may be present as a separate layer, wherein the layer thickness may be a few nanometers, for example less than 10 nm, more preferably less than 5 nm, even more preferably less than 3 nm. The tin dioxide can also be present at least partially in admixture with the titanium dioxide.

Examples of low-refraction layers include metal oxides such as silicon oxide, preferably silicon dioxide (SiO ₂ ), aluminum oxide, preferably Al ₂ O ₃ , boron oxide, preferably boron oxide (B ₂ O ₃ ), metal fluorides such as magnesium fluoride, preferably MgF ₂ , aluminum fluoride , preferably AlF ₃ , cerium fluoride, preferably cerium (III) fluoride (CeF ₃ ), calcium fluoride, preferably CaF ₂ , Metal oxide hydrates such as alumina hydrate AIOOH, silica, preferably SiO ₂ · H ₂ O and / or mixtures thereof.

Preferably, the low refractive index layer comprises silicon dioxide.

If the non-metallic platelet-shaped substrate is coated with only a single metal oxide layer, then it preferably has a high refractive index. Depending on the geometric metal oxide layer thickness, such pearlescent pigments can bring about different color effects, as illustrated in Table 1. Table 1: Typical colors and geometrical layer thicknesses of pearlescent pigments Occupancy / geometric layer thickness colour Silver-white pearlescent pigments TiO ₂ : 40-60 nm silver interference pigments TiO ₂ : 20-40 nm pale blue TiO ₂ : 60-80 nm yellow TiO ₂ : 80 - 100nm red TiO ₂ : 100-140 nm blue TiO ₂ : 120-160 nm green TiO ₂ : 280-320 nm green (3rd order) Color Luster Pigments Fe ₂ O ₃ : 35-45 nm bronze Fe ₂ O ₃ : 45-55 nm copper Fe ₂ O ₃ : 55-65 nm red Fe ₂ O ₃ : 65-75 nm rotviolett Fe ₂ O ₃ : 75-85 nm Red Green Fe ₃ O ₄ black combination pigments TiO ₂ / Fe ₂ O ₃ golds TiO ₂ / Cr ₂ O ₃ green TiO ₂ / Berlin Blue deep blue

If the platelet-shaped transparent substrate of synthetic mica are such pearlescent pigments z. B. under the trade name Symic commercially available (Eckart, 91235 Hartenstein, Germany). Al ₂ O ₃ flakes coated with TiO ₂ and / or iron oxide and appropriately coated SiO ₂ flakes are available, for example, under the trade names Xirallic or Colorstream (Fa. Merck KGaA, Darmstadt, Germany). With TiO ₂ and / or iron oxide coated glass plates are z. B. under the name Luxan (Eckart), under the name Firemist (BASF SE, Ludwigshafen, Germany) or under the name Miraval (Merck) offered.

Pearlescent pigments, based on artificial substrates and characterized by the ratios D ₁₀ , D ₅₀ and D ₉₀ from the cumulative frequency distribution of the volume-averaged size distribution function with a span ΔD = (D ₉₀ -D ₁₀ ) / D ₁₀ of 0.7 to 1.4 according to WO 2009/103322 A1 by their high color purity. These pearlescent pigments are preferably used according to a preferred variant of the invention.

The non-metallic platelet-shaped substrates may also be coated with a multilayered layer structure with or consisting of metal oxide, metal hydroxide, metal suboxide and / or metal oxide hydrate, wherein the order of the layers may be variable. In this case, preference is given to a layer sequence in which at least one high-index layer and at least one low-index layer are arranged in an alternating manner on a substrate. In the alternating arrangement, it is also possible to arrange one or more high-index layers directly above one another and subsequently one or more low-refractive layers directly above one another. However, it is essential that high and low refractive layers occur in the layer structure. Preferably, starting from the platelet-shaped substrate, at least one layer of high, low and high refractive index is arranged, resulting in pearlescent pigments with particularly intense interference colors. Depending on the layer structure and thicknesses, the interference color may be silver or not silver.

In one embodiment, the composite particles of the invention may comprise mixtures of different pearlescent pigments. For example, pearlescent pigments based on z. B. platelet-shaped synthetic mica of different particle size or with different coating. In addition, the support materials with Pearlescent pigments based on different substrates, such. As glass flakes and platelet-shaped synthetic mica, optionally with different coatings, be occupied. A carrier material may thus comprise, for example, both silver and blue pearlescent pigments of the same or different particle size and optionally pearlescent pigments based on different platelet-shaped substrates.

The D ₅₀ values of the pearlescent pigments to be used according to the invention are preferably in a range from 3 to 350 μm, particularly preferably in a range from 5 to 300 μm and very particularly preferably in a range from 6 to 250 μm.

The size distribution curves of the carrier materials and the pearlescent pigments are determined with a device from. Malvern Instruments GmbH, 71083 Herrenberg, Germany, (Mastersizer 2000) according to the manufacturer. For this purpose, the support materials or the pearlescent pigments are measured several times, preferably three times, as an aqueous suspension. From the individual measurement results then averages are formed. The evaluation of the scattered light signals is carried out according to the Mie theory. The D ₁₀ , D ₅₀ and D ₉₀ values are determined by means of laser diffraction. This means that 10%, 50% or 90% of the carrier materials, preferably carrier particles or effect pigments, have a volume-related diameter which is equal to or less than the respectively specified value.

In a further embodiment, instead of and / or in addition to pearlescent pigments, composite particles according to the invention may also be applied to a carrier material, preferably carrier particles. According to a further embodiment, composite particles based on a platelet-shaped hexagonal support material and an approximately spherical support material can be joined together. This happens z. B. by heating the approximately spherical support material with subsequent admixture of the composite particle.

mit L_E1 Helligkeit des glanznahen Messwinkels (E1 = 15° zum Glanzwinkel), L_E2 Helligkeit des Messwinkels zwischen glanznahem und glanzfernen Winkel (E2 = 45° zum Glanzwinkel) und L_E3 Helligkeit des glanzfernen Messwinkels (E3 = 110° zum Glanzwinkel). Je größer der Zahlenwert des Flopindexes ist, desto stärker kommt die winkelabhängige Helligkeitsänderung, also der Hell-/Dunkelflop zum Ausdruck.If black and white cover cards are printed with the composite particles according to the invention, for example by screen printing, a viewer initially perceives a high gloss and glitter effect. Outside the gloss angle, these black and white overlay cards do not appear dark or black due to the transparency of the composite particles of the present invention, as would be the case, for example, with black and white overlay cards printed with opaque glitters. Objectively, this angle-dependent gloss effect or so-called light / dark flop can be described by the flop index. The flop index is defined according to Alman as follows (S. Schellenberger, M. Entenmann, A. Hennemann, P. Thometzek, Paint and Varnish, 04/2007, p. $$\mathrm{flop\; Index}=\mathrm{2}.\mathrm{69}\cdot {\left({\mathrm{L}}_{\mathrm{e}\mathrm{1}}-{\mathrm{L}}_{\mathrm{e}\mathrm{3}}\right)}^{\mathrm{1}.\mathrm{11}}/{{\mathrm{L}}_{\mathrm{e}\mathrm{2}}}^{\mathrm{0}.\mathrm{86}}$$

with L _E1 Brightness of the near-gloss measuring angle (E1 = 15 ° to the glancing angle), L _E2 Brightness of the measuring angle between glaring and off-glare angle (E2 = 45 ° to the glancing angle) and L _E3 Brightness of the glare-distant measuring angle (E3 = 110 ° to the glancing angle). The larger the numerical value of the flop index, the stronger the angle-dependent change in brightness, ie the light / dark flop, is expressed.

Under direct illumination, black-and-white overlay cards which have been printed with the composite particles according to the invention, for example screen-printed or glittered as in bronzing processes, appear very glittering. Under diffused lighting, these black and white cover cards are perceived as grainy. The graininess is determined by the device Byk mac, Byk-Gardner. To assess the graininess, the high-resolution CCD camera captures an image in diffused lighting created by two white-coated hemispheres. The image is analyzed by means of the histogram of the brightness levels, whereby the homogeneity of the light and dark areas is summarized in a granularity value. ( Byk-Gardner, Quality Control for Paints and Plastics, 2011/2012, p. 98 ).

• Mischen von Trägermaterial, vorzugsweise Trägerpartikeln, und wenigstens einem Perlglanzpigment, wobei das Trägermaterial eine wenigstens teilweise erweichte Oberfläche aufweist.

The composite particles according to the invention are obtainable by a process which comprises the following step:

• Mixing of carrier material, preferably carrier particles, and at least one pearlescent pigment, wherein the carrier material has an at least partially softened surface.

According to a preferred variant of the invention, the mixing of carrier material, preferably carrier particles, and at least one pearlescent pigment takes place with heating, wherein the surface of the carrier material, preferably the carrier particles, at least partially softens.

Alternatively, the carrier material, preferably the carrier particles, may also be heated in a first step and then admixed with pearlescent pigment.

The heating of the carrier material, preferably the carrier particle, preferably takes place with movement of the carrier material.

The movement of the carrier material can take place in a mixer or in a fluidized bed.

1. (a) Mischen von Trägermaterial und wenigstens einem Perlglanzpigment unter Bereitstellen einer Mischung,
2. (b) Erwärmen der in Schritt (a) erhaltenen Mischung unter Erhalt der Kompositpartikel,
3. (c) optionales Klassieren der in Schritt (b) erhaltenen Kompositpartikel.

According to a preferred variant of the invention, the method according to the invention comprises the following steps:

1. (a) mixing carrier material and at least one pearlescent pigment to provide a mixture,
2. (b) heating the mixture obtained in step (a) to obtain the composite particles,
3. (c) optionally classifying the composite particles obtained in step (b).

According to a preferred variant of the process according to the invention, the mixing in step (a) and preferably also the heating in step (b) takes place in a mixer in which the carrier material, preferably the carrier particles, and the at least one pearlescent pigment with a peripheral speed of at least 3 m / s, more preferably at least 4 m / s, even more preferably at least 6 m / s.

The heating in step (b) takes place in dependence on the thermal softening properties of the carrier material. Softening in a temperature range from 40 to 230.degree. C., more preferably from 45.degree. C. to 190.degree. C., even more preferably from 50 to 170.degree. C., is preferably carried out with support materials made of or with plastics.

A significant advantage of this manufacturing method lies in its ease of execution. For adhesion of the pearlescent pigments on the support material, the latter need not be pretreated in a complicated manner, nor must an additional adhesion promoter be added. An additional adhesion promoter is not desired according to the invention, since the optical properties of the composite particle can be changed in an undesired manner. Furthermore, there is a risk of incompatibilities of the adhesion promoter with application media. Finally, a separate coating step with a primer is expensive and expensive, especially for a bulk product.

The bond between carrier material, preferably carrier particles, and the at least one pearlescent pigment is achieved exclusively by specific adhesion, wherein the binding to the at least partially softened carrier material surface takes place.

1. (a) Mischen von Trägermaterial und wenigstens einem Perlglanzpigment unter Bereitstellen einer Mischung,
2. (b) Einbringen von Lösemittel in die in Schritt (a) erhaltene Mischung,
3. (c) Verflüchtigen des Lösemittels aus der in Schritt (b) mit Lösemittel behandelten Mischung unter Erhalt der Kompositpartikel,
4. (d) optionales Klassieren, vorzugsweise Schutzklassieren, der in Schritt (b) oder (c) erhaltenen Kompositpartikel.

In a further embodiment of the invention, the method comprises the following steps:

1. (a) mixing carrier material and at least one pearlescent pigment to provide a mixture,
2. (b) introducing solvent into the mixture obtained in step (a),
3. (c) volatilizing the solvent from the solvent-treated mixture in step (b) to obtain the composite particles,
4. (d) optionally classifying, preferably protecting classifying, the composite particles obtained in step (b) or (c).

According to one embodiment of the invention, step (b), the solvent can be supplied as solvent vapor.

According to one embodiment of the invention, step (c) can be carried out with heating, whereby the volatilization of the solvent is favored.

In this variant of the method according to the invention the at least partial softening of the surface of the carrier material, preferably the carrier material particles, takes place by the influence of the solvent, whereby the pearlescent pigments bind to the surface.

The composite particles according to the invention are present in non-dusting form and can be used for plastic coloration, in nail varnishes or in the graphic arts industry. In particular, the composite particles according to the invention can be used for the finishing of wallpapers or printed products, such as e.g. Greeting cards or cartons. This refinement can be done by bronzing, on the other hand in screen or gravure printing. An already printed wallpaper or an already printed printed product can be given a glittering appearance after being bronzed with the composite particles according to the invention. Also, the composite particles according to the invention can be printed in screen or gravure printing on already printed wallpaper or printed matter. The printing process with the composite particles according to the invention can in this case also take place directly when printing a desired motif and does not necessarily take place on an already printed wallpaper or printed product.

Preferably, composite particles based on platelet-shaped carrier materials are applied by means of bronzing, gravure or screen printing. Composite particles based on approximately spherical, lenticular or irregularly shaped support materials are preferably applied by means of bronzing or scattering devices with engraved scoop rollers. The scoop rollers are used in particular to controlled composite particles having an average particle size D ₅₀ of 100 to 2000 microns applied to the respective substrate.

• Kompositpartikel, umfassend ein Trägermaterial, vorzugsweise ein plättchenförmiges hexagonales Trägerpartikel, sowie wenigstens ein Perlglanzpigment, basierend auf Glasplättchen, wobei das Trägermaterial und das wenigstens eine Perlglanzpigment ohne zusätzliches Haftmittel aneinander gebunden vorliegen.

The invention further relates to the following preferred embodiments:

• Composite particles, comprising a carrier material, preferably a platelet-shaped hexagonal carrier particle, and at least one pearlescent pigment, based on glass flakes, wherein the carrier material and the at least one pearlescent pigment are bonded together without additional adhesive.

Composite particles comprising a support material, preferably a platelet-shaped polygonal, preferably hexagonal support particle, and at least one pearlescent pigment based on glass flakes or synthetic mica flakes, wherein the support material and the at least one pearlescent pigment are bonded together without additional adhesive and the proportion of pearlescent pigment in a range of 0.1 to 20 wt .-%, preferably in a range of 0.2 to 15 wt .-%, more preferably in a range of 0.3 to 12 wt .-%, based on the total weight of the composite particle.

Composite particles, comprising a support material, preferably a platelet-shaped polygonal, preferably hexagonal carrier particle of polyethylene terephthalate (PET), and at least one pearlescent pigment, based on glass flakes, obtained by mixing carrier material and pearlescent pigment under heating.

Composite particles, comprising a carrier material, preferably a platelet-shaped polygonal, preferably hexagonal carrier particles of at least two film layers and at least one pearlescent pigment, based on glass flakes, wherein the carrier material and the at least one pearlescent pigment are bonded to each other without additional adhesive.

Composite particles, comprising a carrier material, preferably a platelet-shaped polygonal, preferably hexagonal carrier particles of at least three flat superimposed film layers, wherein on the two outer Foil layers of the carrier material in each case at least one pearlescent pigment is bonded to the carrier material without additional adhesive.

Composite particles, comprising a carrier material of polyvinyl acetate, preferably an approximately spherical carrier particles, and at least one pearlescent pigment, based on glass flakes or synthetic mica flakes, wherein the carrier material and the at least one pearlescent pigment are bonded together without additional adhesive.

Composite particles comprising a carrier material of preferably polyvinyl butyral, preferably a lenticular carrier particle, preferably having a particle size of ≤ 1.5 mm, and at least one pearlescent pigment based on glass flakes or synthetic mica flakes, wherein the carrier material and the at least one pearlescent pigment are bonded together without additional adhesive available.

Composite particles, comprising a first support material, without adhesive bonded to a second, preferably spherical, support material, wherein the first support material of the composite particle and the second support material are different from each other. The first and second carrier materials are preferably different from one another in the geometric form. Alternatively or cumulatively, the first carrier material and the second carrier material may also differ in their material nature, preferably composition.

Composite particles, based on a first, platelet-shaped polygonal, preferably hexagonal, carrier particles, which is coated with pearlescent pigments based on glass flakes or synthetic mica flakes, and wherein the composite particles without adhesive to a second carrier material, preferably an approximately spherical carrier particles, preferably of polyvinyl acetate, with a preferred particle size of ≤ 2 mm, preferably having a particle size of 0.5 to ≤ 1.5 mm. According to a further embodiment of the invention, optionally also on the second, preferably approximately spherical, carrier particles, and pearlescent pigments may be present.

Coating material such as a cosmetic, preferably a nail varnish comprising composite particles.

The following examples and figures serve to further describe the invention and are not intended to be limiting in any respect. All data are to be understood as wt .-%.

characters

• FIG. 1 shows a scanning electron micrograph (SEM) of the composite particle of Example 2 in 50-fold magnification.
• FIG. 2 shows a scanning electron micrograph (SEM) of the composite particle of Example 2 in 200-fold magnification.
• FIG. 3 shows a scanning electron micrograph (SEM) of the composite particle of Example 2 in 200-fold magnification.
• FIG. 4 shows a scanning electron micrograph (SEM) of the composite particle of Example 2 in 500-fold magnification.
• FIG. 5 shows a light micrograph of the composite particle of Example 1 (scattering on black and white cover card) in 50-fold magnification.
• FIG. 6 shows a light micrograph of the composite particle from Example 3 (scattering on black and white cover card) in 50-fold magnification.
• FIG. 7 shows a scanning electron micrograph (SEM) of the composite particle of Example 12 in 100-fold magnification.

Examples I Preparation of the composite particles according to the invention example 1

94% by weight of PET glitter (Crystal Clear 0.008 "45.008E, coated on one side to avoid binding of pearlescent pigments to the coated side, RJA plastics GmbH, 07989 Teichwolframsdorf, Germany, particle size according to the manufacturer's instructions: 200 μm) were used together with 5 % By weight of Luxan C001 (D ₅₀ = 30-35 μm) and 1% by weight of Luxan C261 (D ₅₀ = 28-33 μm), both from Eckart, into a Papenmeier fast blender system from Gebrüder Lödige Maschinenbau GmbH, 33102 Paderborn, Germany, and mixed for 1 minute at a peripheral speed of 8 m / s, followed by a peripheral speed of 13 m / s for 14 minutes and then a peripheral speed of 8 m / s for 7 minutes During the entire mixing process, the mixing vessel was heated with a flow temperature of 150 ° C. After emptying the mixing vessel, the composite particles thus obtained were cooled to room temperature and passed through a vibrating screen of the mesh neat 1000 μm protection class.

Example 2

94% by weight of PET glitter (Crystal Clear 0.016 "45.016E, coated on one side to avoid binding of pearlescent pigments to the coated side, RJA plastics GmbH, particle size according to the manufacturer's instructions: 400 μm) together with 5% by weight of Luxan E001 (D ₅₀ = 85-90 .mu.m) and 1 wt .-% Luxan E261 (D ₅₀ = 80-85 .mu.m), both from Eckart, in a laboratory high-speed mixer system Papenmeier, Fa. Lödige, and one minute at Subsequently, a peripheral speed of 13 m / s was maintained for 19 minutes and then a peripheral speed of 8 m / s for 7 minutes Before and during the entire mixing process, the mixing tank with a flow temperature of 150 ° was used C. After emptying the mixing container, the composite particles thus obtained were cooled to room temperature and classified as protective using a vibrating sieve of mesh size 1000 μm.

Example 3

94% by weight of PET glitter (Crystal Clear 0.025 "45.025E, coated on one side to avoid binding of pearlescent pigments to the coated side, RJA plastics GmbH, particle size according to the manufacturer's instructions: 600 μm) together with 5% by weight of Luxan C001 (D ₅₀ = 30-35) and 1% by weight of Luxan C261 (D ₅₀ = 28-33), both from Eckart, in a laboratory high-speed mixer system Papenmeier, Lödige, and one minute at a peripheral speed Then, a peripheral speed of 13 m / sec was maintained for 22 minutes and then a peripheral speed of 8 m / sec for one minute, followed by stopping the mixing for one minute before a circumferential speed of 8 for one minute This interruption for one minute and subsequent adjustment of a peripheral speed of 8 m / s for one minute was repeated a total of three times before and during the entire mixing process heated container with a flow temperature of 150 ° C. After emptying the mixing container, the composite particles thus obtained were cooled to room temperature and classed protective over a vibrating screen of mesh size 1000 microns.

Example 4

95% by weight of PET glitter (Crystal Clear 0.016 "45.016E, coated on one side to prevent the pearlescent pigments from binding to the coated side, RJA plastics GmbH) together with 5% by weight of Luxan C261 (D ₅₀ = 80%). 85 μm), Eckart, into a laboratory high-speed mixer system Papenmeier, Lödige, and mixed for one minute at a peripheral speed of 8 m / s, followed by a circumferential speed of 13 m / s for 19 minutes and then for 5 minutes The mixing vessel was heated at a flow temperature of 150 ° C. After the mixing vessel had been emptied, the composite particles thus obtained were cooled to room temperature and protected by means of a 1000 μm mesh sieve.

Example 5

95% by weight of PET glitter (Crystal Clear 0.016 "45.016E, coated on one side to avoid binding of pearlescent pigments to the coated side, RJA plastics GmbH) together with 5% by weight of Symic C001, Eckart, in Lödige, a laboratory high-speed mixer system Papenmeier and mixed for a minute at a peripheral speed of 8 m / s was then maintained for 25 minutes, a circumferential speed of 13 m / s and then for 5 minutes, a peripheral speed of 8 m / s Before and during the entire mixing process, the mixing vessel was heated to a flow temperature of 150 ° C. After emptying the mixing vessel, the composite particles thus obtained were cooled to room temperature and protected by a vibration sieve of mesh size 1000 μm.

Example 6

98 wt .-% PVC granules (Optigran TG101, Fa. JSC Veika, Vilnius, Lithuania) were together with 2 wt .-% Luxan E001 (D ₅₀ = 85 - 90 microns), Eckart, in a laboratory high-speed mixer system Papenmeier, Lödige, and mixed for one minute at a peripheral speed of 8 m / s. Subsequently, a peripheral speed of 13 m / s was maintained for 10 minutes and thereafter a circumferential speed of 8 m / s for 5 minutes. Before and during the entire mixing process, the mixing vessel was heated with a flow temperature of 105 ° C. After emptying the mixing container, the composite particles thus obtained were cooled to room temperature and classed protective over a vibrating screen of mesh size 2000 microns.

Example 7

97 wt .-% PVC granules (Optideco 7103 EK1, Fa. JSC VEIKA) were together with 3 wt .-% Luxan F001 (D ₅₀ = 200-210 microns), Eckart, in a laboratory rapid mixer system Papenmeier, Fa Lödige, given and mixed for a minute at a peripheral speed of 8 m / s. Subsequently, a peripheral speed of 13 m / s was maintained for 5 minutes and thereafter a circumferential speed of 8 m / s for 5 minutes. Before and during the entire mixing process, the mixing vessel with a flow temperature of 120 ° C was heated. After emptying the mixing container, the composite particles thus obtained were cooled to room temperature and classed protective over a vibrating screen of mesh size 1000 microns.

Example 8

95 wt .-% polyvinyl butyral granules (PVB granules B75H 0.4-0.7 mm, Polikom, Broshniv Osada, Ukraine) were together with 4 wt .-% Luxan E001 (D ₅₀ = 85 - 90 microns) and 1% by weight of Luxan E261 (D ₅₀ = 80-85 μm), both from Eckart, into a Papenmeier high-speed blender system, Lödige, and mixed for one minute at a peripheral speed of 8 m / s. Subsequently, a peripheral speed of 13 m / s was maintained for 17 minutes and thereafter a peripheral speed of 8 m / s for five minutes. Before and during the entire mixing process, the mixing vessel was heated with a flow temperature of 120 ° C. After emptying the mixing container, the composite particles thus obtained were cooled to room temperature and classed protective over a vibrating screen of mesh size 2000 microns.

Example 9

99% by weight of vinyl acetate homopolymer spheres (VINNAPERL 20, from Wacker Chemie AG, Burghausen, Germany, particle size distribution according to the manufacturer's instructions 0.1-0.8 mm) were used together with 1% by weight of Phoenix PX 4522, Eckart, in a laboratory fast mixer system Papenmeier, Fa. Lödige, and mixed for one minute at a peripheral speed of 8 m / s. Subsequently, a peripheral speed of 13 m / s was maintained for 8 minutes and thereafter a peripheral speed of 8 m / s for three minutes. Before and during the entire mixing process, the mixing vessel was heated with a flow temperature of 90 ° C. After emptying the mixing container, the composite particles thus obtained were cooled to room temperature and classed protective over a vibrating screen of mesh size 2000 microns.

Example 10

99% by weight of vinyl acetate homopolymer spheres (VINNAPERL 20, from Wacker Chemie AG, Burghausen, Germany, particle size distribution according to the manufacturer's instructions 0.1-0.8 mm) were added together with 1% by weight of Luxan C001 from Eckart to a laboratory rapid mixer system Papenmeier, Lödige, and mixed for one minute at a peripheral speed of 8 m / s. Subsequently, a peripheral speed of 13 m / s was maintained for 8 minutes and thereafter a peripheral speed of 8 m / s for three minutes. Before and during the entire mixing process, the mixing vessel was heated with a flow temperature of 90 ° C. After emptying the mixing container, the composite particles thus obtained were cooled to room temperature and classed protective over a vibrating screen of mesh size 2000 microns.

Example 11

94 wt .-% PET glitter (Crystal Black 0.016 "104.016E, coated on one side to avoid the binding of pearlescent pigments to the coated side, Fa. RJA plastics GmbH, particle size according to the manufacturer: 400 microns) were together with 6 wt .-% Luxan E261 (D ₅₀ = 80-85 μm), Eckart, into a laboratory rapid mixer system Papenmeier, Lödige, and mixed for one minute at a peripheral speed of 8 m / s, followed by a circumferential speed of 13 for 19 minutes m / s and then maintained for 7 minutes a peripheral speed of 8 m / s Before and during the entire mixing process, the mixing vessel was heated with a flow temperature of 150 ° C. After emptying the mixing vessel, the resulting composite particles were cooled to room temperature and over a Vibration sieve of mesh size 1000 μm classified protection.

Example 12

94% by weight of PET glitter (Crystal Yellow 0.016 "50.015E, coated on one side to avoid binding of pearlescent pigments to the coated side, RJA plastics GmbH, particle size according to the manufacturer's instructions: 400 μm) together with 6% by weight of Luxan E221 (D ₅₀ = 80-85 μm), Eckart, into a laboratory high-speed mixer system Papenmeier, Lödige, and mixed for one minute at a circumferential speed of 8 m / s, followed by a peripheral speed of 13 for 19 minutes m / s and thereafter maintain a peripheral speed of 8 m / s for 7 minutes before and during the whole Mischvorgangs the mixing vessel was heated with a flow temperature of 150 ° C. After emptying the mixing container, the composite particles thus obtained were cooled to room temperature and classed protective over a vibrating screen of mesh size 1000 microns.

Example 13

89% by weight of vinyl acetate homopolymer spheres (VINNAPERL 20, from Wacker Chemie AG, Burghausen, Germany, particle size distribution according to the manufacturer's instructions 0.1-0.8 mm) were mixed with 10% by weight of PET glitter (Crystal Clear 0.008 ", Fa. RJA plastics GmbH, before cutting the film coated on both sides with polyvinyl butyral by solvent intaglio printing with cylinder configuration of 70 lines / cm and a volume of 14 cm ³ / m ² , Poylvinylbutyral 25 wt .-% in ethanol) in a laboratory Fast mixer system Papenmeier, Fa. Lödige, and mixed for one minute at a peripheral speed of 8 m / s.
Subsequently, a peripheral speed of 13 m / s was maintained for 26 minutes. Subsequently, the mixing process was stopped and 1 wt .-% Luxan C001 (D ₅₀ = 30 - 35 microns), Eckart, added. Thereafter, 20 minutes were mixed at a peripheral speed of 13 m / s. Prior to mixing and mixing, until the addition of Luxan C001, the mixing vessel was heated to a flow temperature of 110 to 125 ° C. Subsequently, the mixing vessel was heated to a flow temperature of 125 to 135 ° C until the end of the mixing process. After emptying the mixing container, the composite particles thus obtained were cooled to room temperature and classed protective over a vibrating screen of mesh size 2000 microns.

Example 14

90% by weight of PET glitter (Crystal Clear 0.08 ", RJA plastics GmbH), before cutting the film on both sides coated with polyvinyl butyral by means of solvent intaglio printing with a cylinder configuration of 70 lines / cm and a volume of 14 cm ³ / m ² , Poylvinylbutyral 25 wt .-% in ethanol) were added together with 10 wt .-% LUXAN C001, Fa. Eckart, in a laboratory rapid mixer system Papenmeier, Fa. Lödige, and mixed for one minute at a peripheral speed of 8 m / s. It was then heated for 12 minutes at a peripheral speed of 13 m / s mixed. Thereafter, a peripheral speed of 8 m / s was maintained for 6 minutes. Before and during the mixing process, the mixing vessel was heated at a flow temperature of 135 ° C.
In a second process step then 10 wt .-% of the mixture thus obtained with 90 wt .-% vinyl acetate homopolymer spheres (VINNAPERL 20, Fa. Wacker Chemie AG, Burghausen, Germany, particle size distribution 0.1 - 0.8 mm) in a Laboratory high speed mixer system Papenmeier, Fa. Lödige, and mixed for one minute at a peripheral speed of 8 m / s. Thereafter, a peripheral speed of 13 m / s was maintained for 29 minutes. Subsequently, a peripheral speed of 8 m / s was maintained for five minutes. Before and during the mixing process, the mixing vessel was heated with a flow temperature of 100 ° C.
After emptying the mixing container, the composite particles thus obtained were cooled to room temperature and classed protective over a vibrating screen of mesh size 2000 microns.

Example 15

88 wt .-% PET glitter (Crystal Clear 0.016 "45.016E, Fa. RJA plastics GmbH, particle size according to the manufacturer: 400 microns, before cutting the film coated on both sides with polyvinyl butyral by solvent intaglio printing with cylinder configuration of 70 lines / cm and a Volume of 14 cm ³ / m ² , polyvinyl butyral 25% by weight in ethanol) together with 10% by weight of Luxan E001 (D ₅₀ = 85-90 μm) and 2% by weight of Luxan E261 (D ₅₀ = 80 85 μm), both from Eckart, into a Papenmeier high-speed mixer system from Lödige, and mixed for one minute at a peripheral speed of 8 m / s, followed by a circumferential speed of 13 m / s for 19 minutes and then For 7 minutes, a peripheral speed of 8 m / s was maintained before and during the entire mixing process, the mixing vessel was heated with a flow temperature of 150 ° C. After emptying the mixing vessel, the resulting composite particles were cooled to room temperature and transferred he classified a vibrating sieve of mesh size 1000 μm.

Comparative Example 1

Polyester Hexagon Glitter Silver 0.008 ", Fa. RJA plastics GmbH.

Comparative Example 2

Polyester Hexagon Glitter Silver 0.016 ", Fa. RJA plastics GmbH.

Comparative Example 3

Polyester Hexagon Glitter Silver 0.025 ", Fa. RJA plastics GmbH.

Comparative Example 4

Crystal Clear 0.008 "45.008E, coated on one side, RJA plastics GmbH.

Comparative Example 5

Crystal Clear 0.016 "45.016E, coated on one side, RJA plastics GmbH.

Comparative Example 6

Crystal Clear 0.025 "45.025E, coated on one side, RJA plastics GmbH.

Comparative Example 7

90% by weight of PET glitter (Crystal Clear 0.016 "45.016E, coated on one side to avoid binding of pearlescent pigments to the coated side, RJA plastics GmbH) was mixed with 5% by weight of Luxan C001 (D ₅₀ = 30-35 Subsequently, 10% by weight of a 1: 1 mixture of Laropal A81, BASF SE, Ludwigshafen, Germany, and isopropanol were added and homogenized again 3 mm on a plate and then dried in a drying oven at 60 ° C. for 15 min .. The slight volatility of the isopropanol, the solids content of the mixture after drying at 100 wt .-%.

II characterization of the composite particles according to the invention IIa particle size measurement

The size distribution curve of the carrier materials and pearlescent pigments was determined using a device from Malvern Instruments GmbH, 71083 Herrenberg (device: Mastersizer 2000) according to the manufacturer's instructions. For this purpose, about 0.1 g of the corresponding support material or pearlescent pigment as an aqueous suspension, without the addition of dispersing aids, with constant stirring by means of a Pasteur pipette in the sample preparation cell of the meter and measured in triplicate. From the individual measurement results, the resulting averages were formed. The evaluation of the scattered light signals was carried out according to the Mie theory, which also includes refractive and absorption behavior of the carrier materials or the pearlescent pigments.

In the context of this invention, the average size D ₅₀ is the D ₅₀ value of the cumulative frequency distribution of the volume-averaged size distribution function as obtained by laser diffraction methods. The D ₅₀ value indicates that 50% of the carrier materials or pearlescent pigments have a diameter which is equal to or less than the stated value, for example 20 μm. Accordingly, the D ₁₀ or D ₉₀ value indicates that 10% or 90% of the carrier materials or pearlescent pigments have a diameter which is equal to or less than the specified value.

IIb determination of the average thickness

The average thickness was determined by means of cross sections of the composite particles according to the invention with the scanning electron microscope Supra 35 (Carl Zeiss AG, 73447 Oberkochen, Germany). In each case at least 100 particles were measured in order to obtain meaningful statistics.

IIc Scanning electron micrographs

The scanning electron micrographs were obtained on the basis of cross-sections of the composite particles according to the invention with the scanning electron microscope Supra 35 (Carl Zeiss AG).

IId light micrographs

Optical micrographs were taken using black and white overlay cards (Leneta Form 605 C, Leneta Company, Inc., Mahwah, New Jersey, USA) with the Axioskop 50 microscope (Carl Zeiss AG). For this purpose, the particles of the respective examples or comparative examples were sprinkled onto the black-and-white cover cards.
Before scattering the composite particles of the inventive examples and the particles according to the comparative examples, the black-and-white registration cards were screen printed (screen PET 1500 30-120 (threads per cm), Fa. Sefar (9410 Heiden, Switzerland) with the solvent-based screen printing binder Libraspeed LIS (Marabu GmbH & Co. KG, 71732 Tamm, Germany) For better printability and substrate wetting the screen printing binder with 0.25 wt .-% Byk 019 and 0.25 wt .-% Dynwet 800 (both BYK Chemie GmbH, 46483 Wesel, Germany), in each case based on the total weight of the screen printing formulation The particles of the Examples or Comparative Examples were then scattered over the screen printing binder at an angle of 45 ° C. Excess effect pigment was knocked off and then at 80 ° C. for 5 minutes dried in a drying oven.

IIe gloss measurements

The gloss measurements were made using black-and-white cover maps (Leneta Form 605 C, Leneta) with the device micro-TRI-gloss μ (Byk-Gardner GmbH, 82538 Geretsried, Germany) according to the manufacturer with a measurement geometry of 20 ° , 60 ° and 85 °, relative to the vertical, each carried out on white and black background. A measurement geometry of 60 ° is suitable for the so-called "medium gloss" in the range of 10 to 70 gloss points, with a higher numerical value in the highlights corresponds to a higher gloss. A measuring geometry of 20 ° is suitable for the so-called "high gloss", ie if the gloss value for the measuring geometry of 60 ° is more than 70 gloss points, measurement is carried out at a measuring geometry of 20 °. A measuring geometry of 85 ° is suitable for the so-called "matt gloss", ie if the gloss value for the measuring geometry of 60 ° is less than 10 gloss points, the measurement geometry is 85 ° measured. (Byk-Gardner, catalog "Quality control for paints and plastics" 2011/2012, p. 16). The gloss values listed in the table below represent averages of five individual measurements each.
For this purpose, the particles of the examples or comparative examples were either sprinkled onto the black and white cover cards as described in Section IId, or the black and white cover cards were hereby screen printed. For the screen printing, a screen printing ink consisting of 15% by weight of XY from the examples and comparative examples and 85% by weight of plastisol PH1046 (from Pharetra Gesellschaft für Textil Kunststoffanwendung mbH & Co. KG, 95152 Selbitz, Germany) was produced. Depending on the particle size, this screen printing ink was screen printed (screen PET 1500 8-300 (threads per cm / thread thickness in μm) or 21-140 (threads per cm / thread thickness in μm), Sefar) on black-and-white Cover cards printed and then dried at 170 ° C in a drying oven for 1 minute. With a particle size of greater than 200 μm, the sieve was PET 1500 8-300, and with a particle size of up to 200 μm, the sieve PET 1500 21-140 was used. Table 2: Gloss values of the particles of the examples or comparative examples on the basis of the black and white cover maps from IId Example / Comparative Example Gloss 20 °, white ° Gloss 20 °, black Gloss 60 °, white Gloss 60 °, black Gloss 85 °, white Gloss 85 °, black example 1 3.0 2.0 3.2 2.2 0.5 0.5 Example 2 4.6 4.8 6.4 5.0 0.6 0.5 Example 3 8.8 7.6 16.2 14.6 2 2 Comparative Example 4 6.0 4.0 5.4 3.4 0.5 0.5 Comparative Example 5 8.4 6.2 8.2 6.0 0.6 0.6 Comparative Example 6 9.8 8.2 13.2 11.6 1.9 2.0 Comparative Example 7 - 4.0 4.6 3.0 0.6 0.5 Example / Comparative Example Gloss 20 °, white ° Gloss 20 °, black Gloss 60 °, white Gloss 60 °, black Gloss 85 °, white Gloss 85 °, black example 1 12.8 9.2 53.0 47.0 70.6 74.4 Example 2 7.8 6.2 44.0 40.4 71.8 71.8 Example 3 7.8 6.0 41.8 39.0 51.8 57.2 Comparative Example 1 11.8 15.0 48.8 56.6 56.4 69.4 Comparative Example 2 7.6 7.2 38.8 38.6 51.6 65.2 Comparative Example 4 11.4 9.4 46.2 44.4 59.0 60.8 Comparative Example 5 8.2 5.0 43.2 35.2 60.6 61.0 Comparative Example 6 5.4 3.6 24.8 25.4 30.6 39.4 Comparative Example 7 4.2 3.6 23.8 24.8 27.2 31.8

IIf determination of the light / dark flop (flop index)

wobei L_E1 für die Helligkeit des glanznahen Messwinkels (E1 = 15° zum Glanzwinkel), L_E2 für die Helligkeit des Messwinkels zwischen glanznahem und glanzfernen Winkel (E2 = 45° zum Glanzwinkel) und L_E3 für die Helligkeit des glanzfernen Messwinkels (E3 = 110° zum Glanzwinkel) steht.
Die in unten stehender Tabelle aufgeführten Werte wurden auf dem weißen Untergrund der Schwarz-Weiß-Deckungskarte vermessen.The light / dark flop (flop index) was determined using the black-and-white cover cards from IIe, which were screen-printed with particles of the examples or comparative examples, using the BYK-mac device (Byk-Gardner). The flop index is defined according to Alman as follows (S. Schellenberger, M. Entenmann, A. Hennemann, P. Thometzek, Paint and Varnish, 04/2007, p. $$\mathrm{flop\; Index}=\mathrm{2}.\mathrm{69}\cdot {\left({\mathrm{L}}_{\mathrm{e}\mathrm{1}}-{\mathrm{L}}_{\mathrm{e}\mathrm{3}}\right)}^{\mathrm{1}.\mathrm{11}}/{{\mathrm{L}}_{\mathrm{e}\mathrm{2}}}^{\mathrm{0}.\mathrm{86}}$$

where L _E1 for the brightness of the near - gloss measuring angle (E1 = 15 ° to the glancing angle), L _E2 for the brightness of the measuring angle between gleam and off - glare angle (E2 = 45 ° to the glancing angle) and L _E3 for the brightness of the off - center measuring angle (E3 = 110 ° to the glancing angle).
The values listed in the table below were measured on the white background of the black and white cover card.

IIg granularity

The granularity G was determined using the black-and-white cover cards from Section IIe, which were screen-printed with the particles of the examples or comparative examples, using the BYK-mac device (Byk-Gardner).

To assess the graininess, the high-resolution CCD camera captures an image in diffused lighting created by two white-coated hemispheres. The image is analyzed by means of the histogram of the brightness levels, whereby the homogeneity of the light and dark areas is summarized in a granularity value. The higher this value is, the more grainy the black-and-white registration card printed with particles of the examples or comparative examples appears under diffuse illumination. The higher the granularity of a black and white cover card printed with the particles of the examples or comparative examples under diffuse light, the more glittering it is visually perceived under direct illumination ( Byk-Gardner, Quality Control for Paints and Plastics, 2011/2012, p. 98 ). Table 4: Brightness L *, Flop Index and Grainy G Example / Comparative Example L *, 15 ° L *, 25 ° L *, 45 ° L *, 75 ° L *, 110 ° flop Index G example 1 100.7 95.1 92.4 91.8 89.1 0.8 3.3 Example 2 100.7 94.3 89.8 90.2 87.9 1.0 4.8 Example 3 101.9 94.2 90.3 89.2 87.2 1.1 3.4 Comparative Example 1 110.1 96.4 86.7 75.2 73.6 3.1 22.5 Comparative Example 2 104.2 90.8 72.9 65.7 59.4 4.6 23.6 Comparative Example 3 103.5 77.8 61.1 58.3 57.0 5.6 22.6

The larger the numerical value of the flop index, the stronger the light / dark flop is expressed. When comparing Examples 1 to 3, it can be seen that the value of the flop index increases with increasing particle size of the composite particles. The same applies to Comparative Examples 1 to 3. A comparison of Examples 1 to 3 with Comparative Examples 1 to 3 shows that in the latter case the value of the flop index is significantly higher. Even with a visual assessment of printed with the comparative examples 1 to 3 black and white cover cards lose these outside the gloss angle their metallic luster and appear dark to a viewer. This optical effect is significantly less pronounced in Examples 1 to 3, which is explained by the transparency of the composite particles according to the invention. Due to this transparency, the white background of the black-and-white backsheet shines through outside the gloss angle.

The higher the numerical value G of the granularity, the more grainy the diffuse light appears, the black-and-white registration card printed with the respective example or comparative example to a viewer. In a comparison of Examples 1 to 3 with Comparative Examples 1 to 3 significantly higher values for the granularity G can be observed in the latter. This is also visible in a visual assessment of the respective black and white cover cards. Comparative Examples 1 to 3 show, in contrast to Examples 1 to 3, a significantly higher, unevenly acting glitter effect, while in Examples 1 to 3 a more homogeneous appearance is perceived.

III Application Examples Application Example 1: Application of Example 1 on a Wallpaper by Screen Printing

For screen printing, a screen printing ink consisting of 15% by weight of the composite particles from Example 1 and 85% by weight of plastisol PH1046 (Pharetra) was prepared. This screen printing ink was printed on an already printed wallpaper by means of screen printing method (sieve PET 1500 18-180 (threads per cm / thread thickness in μm), Fa. Sefar) and then dried at 200 ° C in a drying tunnel.

Application Example 2: Application of Example 2 on a Wallpaper in the Aufstreuverfahren

For the refinement of a wallpaper already printed by means of gravure printing, it was printed with an adhesive layer of Optifoam, Fa. Veika, in the gravure printing process. Subsequently, the composite particles from Example 2 were applied to this wallpaper by means of a Aufrereueinheit. After drying the wallpaper in a drying tunnel at 150 ° C, excess composite particles were sucked off.

Application Example 3: Application of Example 1 on a Wallpaper in an aqueous gravure printing process

For intaglio printing, a gravure ink consisting of 15% by weight of the composite particles from Example 1 and 85% by weight of Rotostar Aqua 400 255 Medium, Eckart, was prepared and treated with water to a pressure viscosity of 30 s in DIN Auslaufbecher No. 4 , Byk-Gardner, discontinued. This gravure ink was printed by gravure printing on an already printed wallpaper and then dried at 150 ° C in a drying tunnel. Application Example 4: Nail Polish INCI name product name Wt .-% Manufacturer example 1 3 Butyl acetates, ethyl acetates, nitrocellulose, isopropyl alcohol International Lacquers Base 12616 98,00 Fa. International Lacquers INCI name product name % By weight Manufacturer Example 3 4 Butyl acetates, ethyl acetates, nitrocellulose, isopropyl alcohol International Lacquers Base 12616 96,00 Fa. International Lacquers INCI name product name Wt .-% Manufacturer Example 2 2 Syncrystal Silver 2 Fa. Eckart Butyl acetates, ethyl acetates, nitrocellulose, isopropyl alcohol International Lacquers Base 12616 96,00 Fa. International Lacquers

Claims (15)

1. Composite particle comprising a carrier material and at least one pearlescent pigment,
   characterised in that
   the carrier material and the at least one pearlescent pigment are present bonded to one another without adhesive, and the pearlescent pigment lies on the surface of the carrier material and is not enveloped or encapsulated by the carrier material.
2. Composite particle as claimed in claim 1,
   characterised in that
   the carrier material has a glass transition temperature.
3. Composite particle as claimed in one of the preceding claims, characterised in that
   the carrier material is platelet-shaped.
4. Composite particle as claimed in one of preceding claims 1 or 2, characterised in that
   the carrier material is approximately spherical, lens-shaped or of an irregular shape.
5. Composite particle as claimed in one of the preceding claims, characterised in that
   the carrier material has a polygonal shape.
6. Composite particle as claimed in one of the preceding claims,
   characterised in that
   the at least one pearlescent pigment is joined to the carrier material with a largely flat contact.
7. Composite particle as claimed in one of the preceding claims, characterised in that
   the at least one pearlescent pigment and the carrier material are joined to one another by a material bond.
8. Composite particle as claimed in one of the preceding claims, characterised in that
   the composite particle comprises a first carrier material, which first carrier material is bonded to a second carrier material without adhesive, and the second carrier material and the first carrier material of the composite particle are different from one another.
9. Composite particle as claimed in one of the preceding claims, characterised in that
   the carrier material is a plastic.
10. Composite particle as claimed in claim 9,
    characterised in that
    the plastic is a thermoplastic or thermoplastic or elastomer.
11. Method of producing a composite particle as claimed in one of the preceding claims,
    characterised in that
    the method comprises the following steps: mixing carrier material and at least one pearlescent pigment, which carrier material has an at least partially softened surface.
12. Use of a composite particle as claimed in one of claims 1 to 9 for coating substrates, preferably wallpaper and printed products.
13. Use of a composite particle as claimed in one of claims 1 to 9 in a coating material or as a coating material.
14. Coating material,
    characterised in that
    it contains composite particles as claimed in one of claims 1 to 9.
15. Coating material as claimed in claim 13,
    characterised in that
    the coating material is a paint, printing ink, varnish or cosmetic.

Images